JP5940855B2 - Laminated body - Google Patents

Description

  In the present invention, a layer composed of a copolymer polycarbonate of isosorbide and aromatic diol is laminated on a polycarbonate resin sheet, and further, if desired, a hard coat layer is laminated, transparency, scratch resistance, flatness, moisture and heat resistance, water absorption resistance It is related with the laminated body which is excellent in.

  Since the polycarbonate resin sheet is excellent in transparency, heat resistance, and mechanical strength, it is used for displays of OA / electronic devices, touch panels, and the like. However, since the polycarbonate resin sheet has a soft surface and is easily scratched, the pencil hardness is only about 2B, and there is a problem that scratches once generated are conspicuous.

In order to improve the surface characteristics, a method of laminating an acrylic resin layer on a polycarbonate resin sheet (for example, Patent Document 1), and a method of performing a hard coat treatment on the acrylic resin layer (for example, patents) are known. Literature 2-4). However, the acrylic resin layer absorbs more moisture than the polycarbonate resin layer, and the dimensional change after moisture absorption becomes larger. Therefore, a laminate in which an acrylic resin layer is provided on one side of a polycarbonate resin, and a laminate in which a hard coat layer is provided on one or both sides of a laminate, the acrylic resin layer becomes convex when exposed to high temperature and high humidity. There is a problem that warping occurs, which has an adverse effect on the machining process.
In addition, a method in which a copolymer polycarbonate is laminated instead of an acrylic resin has been proposed (Patent Document 5). However, there is a problem that the surface characteristics (particularly pencil hardness) are inferior to those of a sheet laminated with an acrylic resin layer.

JP 2007-160892 A JP 2006-103169 A JP 2007-237700 A JP 2008-049623 A JP 2012-025796 A

  An object of the present invention is to provide a laminate excellent in transparency, scratch resistance, flatness, moisture and heat resistance, and water absorption resistance, and particularly suitable for display cover panels and touch panels of OA / electronic devices.

As a result of intensive studies, the present inventors have found that the above object can be achieved by laminating a layer made of a specific copolymer polycarbonate resin on a polycarbonate resin sheet, and have reached the present invention.
That is, the present invention is as follows.

で表される単位（Ａ）と下記式

［式（Ｂ）中、Ｗは単結合、または下記式（Ｗ）

であり、Ｒ_１とＲ_２はそれぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、炭素原子数６〜１２のアリール基、炭素原子数２〜５のアルケニル基、または炭素原子数７〜１７のアラルキル基を表す。また、Ｒ_１とＲ_２が結合して炭素環または複素環を形成しても良い。Ｒ_３とＲ_４はそれぞれ独立に、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素原子数１〜９のアルキル基、炭素原子数１〜５のアルコキシ基、または炭素原子数６〜１２のアリール基を表す。Ｒ_５は１〜９のアルキレン基である。ａは０〜２０の整数を表し、ｂは１〜５００の整数を表す。］
で表される単位（Ｂ）を含み、単位（Ａ）と単位（Ｂ）とのモル比（Ａ／Ｂ）が３０／７０〜９０／１０の共重合ポリカーボネートからなる層を積層した積層体。 1. The following formula having a thickness of 10 to 200 μm is formed on at least one surface of the polycarbonate resin sheet.

Unit (A) represented by the following formula

[In the formula (B), W is a single bond, or the following formula (W)

R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. It represents an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring. R ₃ and R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms. Represents an aryl group of ˜12. R ₅ is an alkylene group of 1 to 9. a represents an integer of 0 to 20, and b represents an integer of 1 to 500. ]
In comprises a unit (B) represented by the unit (A) and the molar ratio of the unit (B) (A / B) is laminated body obtained by laminating a layer made of copolycarbonates 30/70 90/10.

で表される単位（Ａ１）である前項１記載の積層体。
３．積層体の総厚みが０．１〜２．０ｍｍである前項１記載の積層体。
４．共重合ポリカーボネートのガラス転移温度Ｔｇが１１５℃〜１６０℃である前項１記載の積層体。
５．共重合ポリカーボネートの吸水率が０．５％〜１．５％である前項１記載の積層体。
６．共重合ポリカーボネートからなる層上にハードコート層が積層された前項１記載の積層体。
７．ハードコート層が紫外線硬化性塗料から形成されたものである前項６記載の積層体。
８．ハードコート層の厚みが１〜２０μｍである前項６記載の積層体。
９．共重合ポリカーボネート１００重量部に対して、分子量が３５０以上の紫外線吸収剤を０．５〜５．０重量部含有する前項１記載の積層体。
１０．共重合ポリカーボネート１００重量部に対して、リン系熱安定剤０．００１〜０．２重量部含有する前項１記載の積層体。
１１．共重合ポリカーボネート１００重量部に対して、離型剤０．００５〜２．０重量部含有する前項１記載の積層体。
１２．ディスプレイカバーパネルまたはタッチパネルとして使用される前項１〜１１のいずれか１項に記載の積層体。 2. The main unit (A) is the following formula

The laminated body of the preceding clause 1 which is a unit (A1) represented by these.
3. 2. The laminate according to item 1 above, wherein the total thickness of the laminate is 0.1 to 2.0 mm.
4). 2. The laminate according to item 1 above, wherein the glass transition temperature Tg of the copolymer polycarbonate is 115 ° C. to 160 ° C.
5). 2. The laminate according to item 1 above, wherein the water absorption of the copolymer polycarbonate is 0.5% to 1.5%.
6). 2. The laminate according to item 1 above, wherein a hard coat layer is laminated on a layer made of a copolymerized polycarbonate.
7). 7. The laminate according to 6 above, wherein the hard coat layer is formed from an ultraviolet curable paint.
8). 7. The laminate according to item 6 above, wherein the thickness of the hard coat layer is 1 to 20 μm.
9. 2. The laminate according to item 1 above, containing 0.5 to 5.0 parts by weight of an ultraviolet absorber having a molecular weight of 350 or more with respect to 100 parts by weight of the copolymer polycarbonate.
10. 2. The laminate according to item 1 above, containing 0.001 to 0.2 parts by weight of a phosphorus-based heat stabilizer with respect to 100 parts by weight of the copolymer polycarbonate.
11. The laminate according to item 1 above, containing 0.005 to 2.0 parts by weight of a release agent with respect to 100 parts by weight of the copolymer polycarbonate.
12 12. The laminate according to any one of the preceding items 1 to 11, which is used as a display cover panel or a touch panel.

  Since the laminate of the present invention has transparency, scratch resistance, flatness, moisture heat resistance, and water absorption resistance, it is particularly useful for display cover panels and touch panels of mobile devices including mobile phones and smartphones.

Hereinafter, the present invention will be described in detail.
<Polycarbonate resin>
The polycarbonate resin used for the polycarbonate resin sheet of the present invention is an aromatic polycarbonate resin produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method. 2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4- Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone and the like. It is done. A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane series, and bisphenol A is particularly preferred.

Examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
In producing the polycarbonate resin, the above dihydric phenols can be used alone or in combination of two or more thereof, and a molecular weight regulator, a branching agent, a catalyst and the like can be used as necessary.

The molecular weight of the polycarbonate resin is 1.0 × 10 ^{4 to} 10.0 × 10 ⁴ in terms of viscosity average molecular weight, preferably 1.5 × 10 ^{4 to} 4.5 × 10 ⁴ , more preferably 1. 8 × a ^{10 4 ~3.0} × ¹⁰ 4. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin may contain additives as required, for example, heat stabilizers (0.001 to 0.1% by weight) such as phosphites, phosphates, and phosphonates, triazoles, acetophenones, and salicylates. UV absorbers (0.1 to 0.7% by weight) such as tetrabromobisphenol A, low molecular weight polycarbonate of tetrabromobisphenol A, flame retardants such as decabromodiphenyl ether (3 to 15% by weight), colorants, fluorescence You may mix | blend a whitening agent etc.

<Polycarbonate resin sheet>
The method for producing the polycarbonate resin sheet is not particularly limited, and examples thereof include a melt extrusion method and a solution casting method (casting method). A specific method of the melt extrusion method is, for example, that a polycarbonate resin is quantitatively supplied to an extruder, heated and melted, and the molten resin is extruded in a sheet form from a tip of a T die onto a mirror surface roll, and a plurality of rolls. A method is used in which it is taken up while being cooled and cut or wound into an appropriate size when solidified. The specific method of the solution casting method is, for example, casting a solution (concentration 5% to 40%) of polycarbonate resin in methylene chloride from a T-die onto a mirror-polished stainless steel plate, and the temperature is controlled stepwise. The sheet is peeled off while passing through an oven, peeled off, the solvent is removed, and then cooled and wound.

  The thickness of the polycarbonate resin sheet is thicker than the copolymer polycarbonate layer described later, and is preferably in the range of 0.08 to 1.99 mm. The lower limit of the thickness is more preferably 0.1 mm, further preferably 0.2 mm, and particularly preferably 0.3 mm. Further, the upper limit of the thickness is more preferably 1.89 mm, further preferably 1.69 mm, and particularly preferably 1.49 mm. In addition, when it has a hard-coat layer, the upper limit of thickness is preferable 1.98 mm, 1.88 mm is more preferable, 1.68 mm is further more preferable, 1.48 mm is especially preferable.

<Copolymerized polycarbonate>
In the copolymeric polycarbonate of the present invention, the main repeating unit is composed of a unit (A) and a unit (B).

で表される単位（Ａ１）、（Ａ２）および（Ａ３）が例示される。これらは、糖質由来のエーテルジオールであり、自然界のバイオマスからも得られる物質で、再生可能資源と呼ばれるものの１つである。単位（Ａ１）、（Ａ２）および（Ａ３）は、それぞれイソソルビド、イソマンニド、イソイディッドと呼ばれる。イソソルビドは、でんぷんから得られるＤーグルコースに水添した後、脱水を受けさせることにより得られる。その他のエーテルジオールについても、出発物質を除いて同様の反応により得られる。 (Unit (A))
The unit (A) is derived from an aliphatic diol having an ether group. As the unit (A), the following formula having a stereoisomer relationship

Are represented by units (A1), (A2) and (A3). These are saccharide-derived ether diols that are also obtained from natural biomass and are one of the so-called renewable resources. Units (A1), (A2), and (A3) are called isosorbide, isomannide, and isoidide, respectively. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  Among isosorbide, isomannide, and isoidide, a unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is particularly preferable because of ease of production and excellent heat resistance.

(Unit (B))
The unit (B) is a carbonate unit having an o-methyl substituted aromatic structure. In the unit (B), W is selected from a single bond or the following formula (W).

In the formula, R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. An aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms is represented. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring.

  Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, and an octyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a heptoxy group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, a naphthyl group, and a fluorene group. Examples of the alkenyl group having 2 to 5 carbon atoms include ethenyl group, propenyl group, butenyl group, heptenyl group, hexynyl group, octynyl group and the like. Examples of the aralkyl group having 7 to 17 carbon atoms include a benzyl group.

R ₃ and R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms. Represents an aryl group of ˜12. Examples of the alkyl group having 1 to 9 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a heptyl group, a hexyl group, and an octyl group. Examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a heptoxy group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a methylphenyl group, a naphthyl group, and a fluorene group.

R ₅ is an alkylene group having 1 to 9 carbon atoms. Examples of the alkylene group having 1 to 9 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an octamethylene group.
a represents an integer of 0 to 20, and b represents an integer of 1 to 500.

  As the unit (B), 3,3′-dimethyl (1,1′-biphenyl) -4,4′diol, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 2,2-bis ( 4-hydroxy-3-methylphenyl) propane (hereinafter abbreviated as bisphenol C), 2,2-bis (4-hydroxy-3-methylphenyl) butane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) -3,3,5-trimethylcyclohexane, 2, 2-bis (4-hydroxy-3-methylphenyl) pentane, 2,2-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxy- - units derived from or methyl phenyl) -4-isopropyl cyclohexane, and the like. Among them, units derived from bisphenol C, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 3,3′-dimethyl (1,1′-biphenyl) -4,4′diol are pencil hardnesses. From the viewpoint of heat resistance and moldability, it is preferable. Two or more of these may be used in combination.

(composition)
The copolymeric polycarbonate resin includes units (A) and units (B) as main repeating units, and the molar ratio (A / B) of units (A) to units (B) is 30/70 to 99/1. is there. When the molar ratio (A / B) is in the range of 30/70 to 99/1, the pencil hardness increases and the heat resistance also increases. The molar ratio (A / B) between the preferred unit (A) and the unit (B) is in the range of 30/70 to 90/10, more preferably in the range of 40/60 to 90/10, still more preferred. Is 40/60 to 80/20 because the pencil hardness is easily set to 2H or more. The molar ratio (A / B) is measured and calculated by proton NMR of JNM-AL400 manufactured by JEOL.

The main unit in the present invention is a total of units (A) and (B) of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, based on all repeating units. Preferably it is 100 mol%.
The copolymer polycarbonate resin may contain 30 mol% or less, preferably 20 mol% or less, more preferably 10 mol% or less of units other than the unit (A) and the unit (B). Examples of other units include units derived from linear aliphatic diol compounds, units derived from alicyclic diols, units derived from aromatic dihydroxy compounds, and mixtures thereof.

  Examples of linear aliphatic diol compounds include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol. 1,8-octanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated And dioleyl glycol. Of these, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and 1,10-decanediol are preferable. These linear aliphatic diols may be used alone or in combination of two or more.

  Examples of the alicyclic diol include cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and 1,2- Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, norbornanedimethanol such as 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, tricyclo Decanedimethanol, pentacyclopentadecanedimethanol, 1,3-adamantanediol, 2,2-adamantanediol, decalindimethanol, and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4 , , 10-tetraoxaspiro [5.5] undecane. Among these, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5. 5] Undecane is preferred. These alicyclic diols may be used alone or in combination of two or more.

  As aromatic dihydroxy compounds, 4,4′-biphenol, 3,3 ′, 5,5′-tetrafluoro-4,4′-biphenol, α, α′-bis (4-hydroxyphenyl) -o- Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (usually referred to as “bisphenol M”), α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-bis (1,1,1,3,3,3-hexafluoroisopropyl) benzene, 9,9-bis (4-hydroxyphenyl) fluorene, 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-fluoro-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-trifluoromethylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (3-fluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) perfluorocyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4, 4'-dihydroxydiphenyl sulfoxide, 4,4 ' Dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-diphenyl sulfide, 4,4′-dihydroxy -3,3'-diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyl sulfone, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (usually referred to as “bisphenol A”), 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy) Phenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydro) Sea 3-phenylphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis ( 4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxy-3-methylphenyl) decane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafur Oropropane (usually referred to as “bisphenol AF”), 2,2-bis (4-hydroxy-3-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) -1,1,1 , 3,3,3-hexafluoropropane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane And 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) include propane.

  Among the above, bisphenol M, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, bisphenol A, bisphenol AF, and 1,1-bis (4-hydroxyphenyl) decane are preferred. These aromatic diols may be used alone or in combination of two or more.

(Viscosity average molecular weight)
The molecular weight of the copolycarbonate is 1.0 × 10 ^{4 to} 10.0 × 10 ⁴ , preferably 1.0 × 10 ^{4 to} 4.5 × 10 ⁴ , more preferably 1 in terms of viscosity average molecular weight. 0.0 × 10 ^{4 to} 3.0 × 10 ⁴ . The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of a copolymerized polycarbonate in 100 ml of methylene chloride at 20 ° C. into the following equation.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(Glass transition temperature: Tg)
The glass transition temperature (Tg) of the copolymerized polycarbonate is preferably 115 to 160 ° C, more preferably 115 to 150 ° C. When the Tg is 115 ° C. to 160 ° C., the heat resistance stability and moldability are good when used as an optical molded body, which is preferable.
When the glass transition temperature (Tg) of the copolymerized polycarbonate is 115 ° C. or higher, the heat resistance and the heat-and-moisture resistance are preferably sufficient. Moreover, it is preferable that the glass transition temperature (Tg) is 160 ° C. or less because the moldability during injection molding is good.
The glass transition temperature (Tg) is measured at 29 ° C./min using a 2910 type DSC manufactured by TA Instruments Japan.

(Water absorption rate)
The water absorption of the copolymer polycarbonate is preferably in the range of 0.5 to 2.0%, more preferably in the range of 0.5 to 1.5%.
The water absorption of the copolymer polycarbonate in the present invention is measured as follows. Using a copolymer polycarbonate molded plate as a test piece, the test piece was left in a constant temperature and humidity chamber at 85 ° C. and 0% RH for 24 hours, then taken out and left at room temperature for 10 minutes, and then weighed with a balance. To dry weight. Next, the test piece was left in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 120 hours, then taken out and further left at room temperature for 10 minutes, and then the weight was measured with a balance to obtain a water absorption weight. The water absorption was determined by the following formula.
Water absorption [%] = (Water absorption weight [g] −Dry weight [g]) / Dry weight [g] × 100 [%]

(Pencil hardness)
The pencil hardness of the copolymer polycarbonate is preferably 2H or more.
The disadvantage is that plastic is relatively soft and easily scratched. Although the pencil hardness of bisphenol-A-PC is low, it can be easily understood that if the surface hardness of the molded body can be increased to 2H or more in terms of pencil hardness, scratches entering the surface of the molded body can be extremely suppressed. Let's go.
And such a hard pencil hardness of 2H or more uses an isosorbide component in the unit (A) as a main repeating unit as described above, and further uses an o-methyl-substituted aromatic component in the unit (B). It can obtain by making the molar ratio into a specific range.

  Incidentally, the pencil hardness in the present invention is a hardness that does not leave any scratches even when the polycarbonate resin of the present invention is rubbed with a pencil having each pencil hardness. Specifically, the pencil hardness used for the surface hardness test of the coating film that can be measured according to JIS K-5600 is preferably used as an index. Pencil hardness becomes soft in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, 6B, the hardest is 9H, The soft one is 6B.

(Method for producing copolymer polycarbonate)
The copolymer polycarbonate resin is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a diol component with a carbonate precursor such as a carbonic acid diester. Next, basic means for these manufacturing methods will be briefly described.

  The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, you may add a terminal stopper, antioxidant, etc. as needed.

  Examples of the carbonic acid diester used in the transesterification include esters such as an aryl group having 6 to 12 carbon atoms and an aralkyl group which may be substituted. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate and m-cresyl carbonate. Of these, diphenyl carbonate is particularly preferred. The amount of diphenyl carbonate used is preferably 0.97 to 1.10 mol, more preferably 1.00 to 1.06 mol, per 1 mol of the total of dihydroxy compounds.

In the melt polymerization method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and metal compounds.
As such compounds, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, quaternary ammonium hydroxides, and the like of alkali metals and alkaline earth metals are preferably used. It can be used alone or in combination.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, Sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus Examples include dilithium oxyhydrogen, disodium phenylphosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium salt, 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt and the like.

  Alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, diacetate Barium and the like are exemplified.

  Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl groups, etc., such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Can be mentioned. Further, tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole can be used. Moreover, bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate and the like are exemplified.

Examples of metal compounds include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, and the like. These compounds may be used alone or in combination of two or more.
The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² equivalent, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ equivalent, more preferably 1 × with ^respect to 1 mol of the diol component. It is selected in the range of 10 ⁻⁷ to 1 × 10 ⁻³ equivalents.

  In addition, a catalyst deactivator can be added at a later stage of the reaction. As the catalyst deactivator to be used, a known catalyst deactivator is effectively used. Among them, sulfonic acid ammonium salt and phosphonium salt are preferable. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid and salts of paratoluenesulfonic acid such as tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

  Further, as esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, Octyl paratoluenesulfonate, phenyl paratoluenesulfonate and the like are preferably used. Among these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used.

The amount of the catalyst deactivator used is preferably 0.5 to 50 mol per mol of the catalyst when at least one polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds is used. It can be used in a proportion, more preferably in a proportion of 0.5 to 10 mol, still more preferably in a proportion of 0.8 to 5 mol.
Copolycarbonate resins are heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, UV absorbers as needed and necessary. Additives such as agents and mold release agents can be blended.

(Additive)
For the copolymerized polycarbonate, a phosphorus-based heat stabilizer, a release agent, an ultraviolet absorber, etc. are preferably used as necessary. Other additives include tetrabromobisphenol A, low molecular weight polycarbonate of tetrabromobisphenol A, decabromo. You may mix | blend flame retardants (3-15 weight%), such as a diphenyl ether, a coloring agent, a fluorescent whitening agent.

  Examples of the phosphorous heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite Phyto, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erisrito Diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol di Phosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, Dipropyl benzenephosphonate, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphos Knight, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, Examples thereof include bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite.

  Among them, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4 , 4′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3 '-Biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite And tris (2,4-di-tert-butylphenyl) phosphite is particularly preferably used. As content of a phosphorus-type heat stabilizer, 0.001-0.2 weight part is preferable with respect to 100 weight part of copolymer polycarbonate, 0.0015-0.1 weight part is more preferable, 0.002-0 0.05 parts by weight is more preferable, and 0.002 to 0.01 parts by weight is particularly preferable.

  As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid. The ester of the monohydric alcohol and the fatty acid is preferably an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. The partial ester or total ester of a polyhydric alcohol and a fatty acid is preferably a partial ester or a total ester of a polyhydric alcohol having 1 to 25 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.

  Specific examples of the monohydric alcohol, saturated fatty acid and ester include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like, and stearyl stearate is preferable.

  Specific examples of partial esters or total esters of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetra Examples include stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate and the like.

  Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.

The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
As content of a mold release agent, the range of 0.005-2.0 weight part is preferable with respect to 100 weight part of copolymer polycarbonate, The range of 0.01-1.0 weight part is more preferable, 0.02 The range of -0.5 part by weight is more preferable, and the range of 0.03-0.1 part by weight is particularly preferable.

  An ultraviolet absorber can be added to the copolymer polycarbonate for the purpose of imparting weather resistance. The molecular weight of the ultraviolet absorber is preferably 350 or more, more preferably 400 or more and 1000 or less, preferably 0.5 to 5.0 parts by weight, more preferably 100 parts by weight of the copolymer polycarbonate. 0.8 to 3.0 parts by weight can be blended. By setting the molecular weight and blending amount of the ultraviolet rays within the above ranges, it is possible to prevent the contamination of the apparatus due to the transpiration of the ultraviolet absorbent and to increase the productivity.

Examples of the ultraviolet absorber include benzotriazole, triazine, benzophenone, and benzoxazine. For example, as the benzotriazole ultraviolet absorber, 2,2′-methylenebis [4- (1,1,3,3 -Tetramethylbutyl) -6- [2H-benzotriazol-2-yl] phenol]], 2,2'-methylenebis [6- (benzotriazol-2-yl) -4-tert-octylphenol], 2- [ 2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H- Benzotriazole and the like can be mentioned, and as the triazine ultraviolet absorber, 2,4-diphenyl-6- (2-hydro Ci-4-methoxyphenyl) -1,3,5-triazine, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyl) Oxy) phenol,
And so on.

<Copolymerized polycarbonate layer>
Any method may be used for laminating the copolymerized polycarbonate layer on the surface of the polycarbonate resin sheet, and it is particularly preferable to carry out by a thermocompression bonding method or a coextrusion method.
Any method can be adopted as the thermocompression bonding method. For example, a method in which a copolymerized polycarbonate film and a polycarbonate resin sheet are thermocompression bonded with a laminating machine or a press machine, or a copolymerized polycarbonate film is thermocompression bonded to a polycarbonate resin sheet immediately after extrusion. A method is preferred, and a method of continuously thermocompression bonding to a polycarbonate resin sheet immediately after extrusion is industrially advantageous. The thermocompression bonding conditions in this case vary depending on the thickness of the polycarbonate resin sheet or the copolymerized polycarbonate film, the state of the crimping surface, etc., and cannot be specified in general, but the temperature near or above the glass transition point of the copolymerized polycarbonate film, usually Glass transition point of copolymerized polycarbonate film −10 ° C. to glass transition point + 150 ° C., preferably glass transition point −5 ° C. to glass transition point + 100 ° C., about 0.05 to 5 kg / cm ² , preferably 0.1 to 1 kg Thermocompression bonding is possible by applying a pressure of about / cm ² .

  There are no particular limitations on the method for producing the copolymer polycarbonate film, and examples thereof include a melt extrusion method and a solution casting method (casting method). A specific method of the melt extrusion method is, for example, supplying a fixed amount of copolymer polycarbonate to an extruder, melting by heating, and extruding a molten resin from a front end portion of a T-die into a sheet shape on a mirror surface roll to form a plurality of rolls. Then, it is taken out while being cooled, and when solidified, it is cut into an appropriate size or wound up. A specific method of the solution casting method is, for example, casting a solution (concentration 5% to 40%) of a copolymerized polycarbonate in methylene chloride from a T die onto a mirror-polished stainless steel plate, and controlling the temperature stepwise. The film is peeled off while passing through the oven, further peeled off, the solvent removed, and then cooled and wound up.

  In the coextrusion method, a copolycarbonate is melt-extruded at a glass transition point to a glass transition point + 230 ° C., preferably at a glass transition point + 50 ° C. to a glass transition point + 200 ° C. with an auxiliary extrusion, and a polycarbonate resin is obtained with a main extrusion. The glass transition point to the glass transition point + 230 ° C., preferably the glass transition point + 50 ° C. to the glass transition point + 200 ° C. can be melt extruded and laminated by extrusion by a known method such as a multi-manifold method or a feed block method.

  The thickness of the copolymer polycarbonate layer is in the range of 10 to 200 μm, preferably in the range of 20 to 100 μm, and more preferably in the range of 30 to 70 μm. If it is too thin, scratches such as scratches will reach the polycarbonate resin sheet of the base material and sufficient scratch resistance will not be obtained, and if it is too thick, impact resistance will be reduced.

<Hard coat layer>
In the present invention, a hard coat layer can be laminated on the surface of the copolymerized polycarbonate layer as desired.
The hard coat layer is not particularly limited in material, lamination method and the like as long as it has sufficient adhesion without impairing transparency. In general, methods such as applying a curable coating that cures by heat, ultraviolet rays, electron beam, etc., physical vapor deposition, chemical vapor deposition, etc. are mentioned. Is preferred.

  The ultraviolet curable coating is not particularly limited as long as it is a composition containing an ultraviolet curable resin and a photopolymerization initiator. Examples of the ultraviolet curable resin include urethane acrylate, epoxy acrylate, polyether acrylate, polyester acrylate, glycidyl compound, alicyclic epoxy compound, and oxetane compound. As photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2-methyl-1-[(4-methylthio) phenyl] -2-morpholinopropan-1-one, benzophenone, 4-benzoyl-4'-methylphenyl sulfide, 2,4-diethylthioxanthone and the like. . Moreover, you may add a dilution solvent, an antifoamer, a leveling agent, an antistatic agent, etc. to this composition.

As a coating means for laminating a hard coat layer using an ultraviolet curable paint, any method such as a spray coating method, a flow coating method, a dipping method, a roll coating method or a bar coating method may be used. From the viewpoint, a roll coating method and a bar coating method are more preferable. Moreover, a hard-coat layer may be formed only on one side according to a use, or may be laminated | stacked on both surfaces.
The thickness of the obtained hard coat layer is preferably in the range of 1 to 20 μm, more preferably in the range of 1.5 to 15 μm, and still more preferably in the range of 2 to 10 μm. When the thickness of the hard coat layer is 1 μm or more, sufficient scratch resistance is obtained, and when it is 20 μm or less, the warpage caused by curing shrinkage is reduced, and the display cover panel or touch panel of OA / electronic devices is used. It is suitable for.

<Laminate>
The laminate of the present invention is a laminate excellent in transparency, scratch resistance, flatness, moist heat resistance, and water absorption resistance.
The thickness of the laminate is preferably in the range of 0.1 to 2.0 mm, and particularly in the range of 0.4 to 1.5 mm when used for a display or a touch panel of an OA device.
As transparency of a laminated body, it evaluates by the total light transmittance value and haze value based on JISK7361-1 and JISK7136. The total light transmittance value of the laminate is preferably 85% or more, more preferably 90% or more. Further, the haze value is preferably 1.0% or less, and more preferably 0.5% or less.
The scratch resistance of the laminate is evaluated by pencil hardness according to JIS K 5600. The scratch resistance of the laminate is preferably HB or more, more preferably H or more, further preferably 2H or more, and particularly preferably 4H or more.

  Hereinafter, although an example is given and explained in detail, the present invention is not limited to this unless it exceeds the purpose. In addition, the performance evaluation in an Example and a comparative example followed the following method.

(1) Glass transition temperature (Tg)
A 2910 type DSC manufactured by TA Instruments Japan Co., Ltd. was used, and the temperature was increased at a rate of temperature increase of 20 ° C./min.

(2) Water absorption rate Using a copolymer polycarbonate molded plate as a test piece, the test piece was left in a constant temperature and humidity chamber at 85 ° C. and 0% RH for 24 hours and then taken out and further left at room temperature for 10 minutes. The weight was measured to obtain a dry weight. Next, the test piece was left in a constant temperature and humidity chamber at 85 ° C. and 85% RH for 120 hours, then taken out and further left at room temperature for 10 minutes, and then the weight was measured with a balance to obtain a water absorption weight. The water absorption was determined by the following formula.
Water absorption [%] = (Water absorption weight [g] −Dry weight [g]) / Dry weight [g] × 100 [%]

(3) Transparency The total light transmittance value and haze value of the laminate were measured according to JIS K 7361-1 and JIS K 7136.

(4) Scratch resistance The laminate was measured for pencil hardness under a load of 750 g in accordance with JIS K 5600.

(5) Evaluation method of flatness The laminate is cut into a size of 50 mm in length and 100 mm in width and left for 4 hours in a temperature 23 ° C. and humidity 50% RH environment, and then the laminate is on the copolymer polycarbonate layer side. Then, the floating amount of the four corners was measured, and the maximum floating amount was taken as the evaluation result. In addition, the floating amount which makes the copolymer polycarbonate layer side convex is positive.

(6) Evaluation method of moisture and heat resistance The laminate was cut into a size of 50 mm in length and 100 mm in width and left for 24 hours in a temperature 85 ° C. and humidity 85% RH environment, and then in a temperature 23 ° C. and humidity 50% RH environment. After standing for 4 hours, the laminate was laid flat so that the copolymer polycarbonate layer side was up, and the total amount of lift at the four corners and the middle point was measured. The maximum lift was taken as the evaluation result. In addition, the floating amount which makes the copolymer polycarbonate layer side convex is positive.

(7) Evaluation method of water absorption The laminate was cut into a size of 50 mm length × 100 mm width, left at 25 ° C. for 72 hours, and then left at a temperature of 23 ° C. and a humidity of 50% RH for 4 hours. The body was placed flat so that the copolymer polycarbonate layer side was on top, and the total amount of lift at the four corners and the middle point was measured. The maximum lift was taken as the evaluation result. In addition, the floating amount which makes the copolymer polycarbonate layer side convex is positive.

(8) Adhesion of hard coat layer 11 cuts are made vertically and horizontally with a cutter on the hard coat layer to make 100 squares, and this is made of cello tape (registered trademark) After affixing the adhesive tape), it was peeled off at a stretch in the direction of 90 °. The hard coat layer did not peel off, and the number of remaining squares was counted.

<Example A-1>
(Manufacture of copolymer polycarbonate)
351 parts of isosorbide (hereinafter abbreviated as ISS), 264 parts of 2,2-bis (4-hydroxy-3-methylphenyl) propane (hereinafter abbreviated as BPC), 749.7 parts of diphenyl carbonate (hereinafter abbreviated as DPC), and catalyst As a result, 0.8 × 10 ⁻² parts of tetramethylammonium hydroxide and 0.6 × 10 ⁻⁴ parts of sodium hydroxide were heated to 180 ° C. in a nitrogen atmosphere and melted. Thereafter, the degree of vacuum was adjusted to 13.4 kPa over 30 minutes. Thereafter, the temperature was raised to 250 ° C. at a rate of 60 ° C./hr, held at that temperature for 10 minutes, and then the degree of vacuum was set to 133 Pa or less over 1 hour. The reaction is carried out with stirring for a total of 6 hours. After completion of the reaction, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid twice the amount of the catalyst is added to deactivate the catalyst, and then discharged from the bottom of the reaction tank under nitrogen pressure. While being cooled in a water bath, it was cut with a pelletizer to obtain pellets (viscosity average molecular weight; 18,500) (resin A-1).

(Manufacture of laminates)
The polycarbonate resin constituting the polycarbonate resin sheet is melted by a single screw extruder having a screw diameter of 40 mm, and the copolymer polycarbonate forming the copolymer polycarbonate layer is melted by a single screw extruder having a screw diameter of 30 mm, and the feed block method is used. Laminated in two layers, extruded through a T-shaped die with a set temperature of 280 ° C., and the resulting sheet is cooled with a mirror-finished roll, polycarbonate resin (trade name: Panlite, Bisphenol A, manufactured by Teijin Chemicals Limited) The laminated body shown in Table 1 which laminated | stacked the copolymer polycarbonate (resin A-1) on the single side | surface of the viscosity average molecular weight 22,000 polycarbonate resin obtained from 1) was obtained. Table 2 shows the performance evaluation results of the obtained laminate.

<Examples A-2, A-5, A-6>
Except that the amounts of ISS and BPC were changed to ISS 250.5 parts and BPC 439.7 parts, the same operation as in Example A-1 was performed to obtain pellets (viscosity average molecular weight; 19,400) (resin A -2, A-5, A-6). Moreover, the laminated body was created by the method similar to Example A-1, the obtained laminated body is shown in Table 1, and a performance evaluation result is shown in Table 2.

<Example A-3>
Except for changing to 1,1-bis (4-hydroxy-3-methylphenyl)) cyclohexane (hereinafter abbreviated as OCZ) instead of BPC and changing the amounts of ISS and OCZ to ISS 250.5 parts and OCZ 508.5 parts. The same operation as in Example 1 was performed to obtain pellets (viscosity average molecular weight; 19,100) (Resin A-3). Moreover, the laminated body was created by the method similar to Example A-1, the obtained laminated body is shown in Table 1, and a performance evaluation result is shown in Table 2.

<Example A-4>
Instead of BPC, 3,3′-dimethyl (1,1′-biphenyl) -4,4 ′ diol (hereinafter abbreviated as OCBP) was changed, and the amounts of ISS and OCBP were ISS 250.5 parts and OCBP 367.3 parts. Except for the above, the same operation as in Example 1 was performed to obtain pellets (viscosity average molecular weight; 18,400) (Resin A-4). Moreover, the laminated body was created by the method similar to Example A-1, the obtained laminated body is shown in Table 1, and a performance evaluation result is shown in Table 2.

<Example A-7>
2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- [2H-benzotriazol-2-yl] as an ultraviolet absorber with respect to 100 parts by weight of the resin A-2 Phenol]] (made by ADEKA, trade name: ADK STAB LA-31), 1.0 part by weight, tris (2,4-di-tert-butylphenyl) phosphite (Ciba Specialty Chemicals) as a phosphorus-based heat stabilizer (Product: Irgafos 168) and 0.01 parts by weight of stearic acid monoglyceride (Riken Vitamin Co., Ltd .: Riquemar S-100A) as a release agent were added to obtain pellets (resin A-7). . Moreover, the laminated body was created by the method similar to Example A-1, the obtained laminated body is shown in Table 1, and a performance evaluation result is shown in Table 2.

<Comparative Example A-1>
The polycarbonate resin constituting the polycarbonate resin sheet is melted by a single screw extruder having a screw diameter of 40 mm, and the acrylic resin forming the acrylic resin layer is melted by a single screw extruder having a screw diameter of 30 mm, and two layers are formed by a feed block method. And is extruded through a T-shaped die with a set temperature of 280 ° C., and the obtained sheet is cooled with a mirror-finished roll, and obtained from polycarbonate resin (manufactured by Teijin Chemicals Ltd., trade names: Panlite, Bisphenol A). The laminated body shown in Table 1 in which an acrylic resin (trade name: Acrypet VH001 manufactured by Mitsubishi Rayon Co., Ltd.) was laminated on one side of the obtained polycarbonate resin having a viscosity average molecular weight of 22,000 was obtained. Table 2 shows the performance evaluation results of the obtained laminate.

<Comparative Example A-2>
Polycarbonate sheet shown in Table 1 (Comparative Example A-2) (manufactured by Teijin Chemicals Ltd., trade name: Panlite sheet PC-1151, formed from a polycarbonate resin having a viscosity average molecular weight of 24,000 obtained from bisphenol A) Sheet). The performance evaluation results are shown in Table 2 (Comparative Example A-2).

<Examples B-1 to B-7>
(Manufacture of laminates)
The polycarbonate resin constituting the polycarbonate resin sheet is a single screw extruder having a screw diameter of 40 mm, and the copolymer polycarbonate (resins A-1 to A-7) forming the copolymer polycarbonate layer is a single screw extruder having a screw diameter of 30 mm. Each was melted with a feed block method, laminated into two layers, extruded through a T-die at a set temperature of 280 ° C., and the resulting sheet was cooled with a mirror-finished roll, and Table 3 (Example B- 1 to B-7) on one side of a polycarbonate resin (manufactured by Teijin Chemicals Ltd., trade name: Panlite, a polycarbonate resin having a viscosity average molecular weight of 22,000 obtained from bisphenol A). 1-A-7) were laminated. The resulting laminate was coated with an ultraviolet curable coating (Shin Nakamura Chemical Co., Ltd. KCR-) using a metal bar coater so as to have the film thickness shown in Table 3 (Examples B-1 to B-7). 8502) was coated on the copolymerized polycarbonate layer, and then cured using an ultraviolet irradiation device so as to obtain an integrated light amount of 600 mJ / cm ² to obtain a laminate. The performance evaluation results of the obtained laminate are shown in Table 4 (Examples B-1 to B-7).

<Comparative Example B-1>
The polycarbonate resin constituting the polycarbonate resin sheet is melted by a single screw extruder having a screw diameter of 40 mm, and the acrylic resin forming the acrylic resin layer is melted by a single screw extruder having a screw diameter of 30 mm, and two layers are formed by a feed block method. And is extruded through a T-shaped die with a set temperature of 280 ° C., and the obtained sheet is cooled with a mirror-finished roll, and obtained from polycarbonate resin (manufactured by Teijin Chemicals Ltd., trade names: Panlite, Bisphenol A). The laminated body which laminated | stacked acrylic resin (Mitsubishi Rayon Co., Ltd. brand name: Acrypet VH001) on the single side | surface of the obtained viscosity average molecular weight 22,000 polycarbonate resin was obtained. Using a metal bar coater, an acrylic curable coating (KCR-8502 manufactured by Shin-Nakamura Chemical Co., Ltd.) was acrylic on the resulting laminate so as to have the film thickness shown in Table 3 (Comparative Example B-1). After coating on the resin layer, it was cured using an ultraviolet irradiation device so as to obtain an integrated light amount of 600 mJ / cm ² to obtain a laminate. The performance evaluation results of the obtained laminate are shown in Table 4 (Comparative Example B-1).

<Comparative Example B-2>
Using a metal bar coater on a polycarbonate sheet (manufactured by Teijin Chemicals Ltd., trade name: Panlite sheet PC-1151), an ultraviolet curable coating material is formed so as to have the film thickness shown in Table 3 (Comparative Example B-2). (Shin-Nakamura Chemical Co., Ltd. KCR-8502) was applied, and then cured using an ultraviolet irradiation device so as to obtain an integrated light amount of 600 mJ / cm ² to obtain a laminate. The performance evaluation results of the obtained laminate are shown in Table 4 (Comparative Example B-2).

  The laminate of the present invention is useful as a display cover panel or touch panel for OA / electronic devices.

Claims (12)

The following formula having a thickness of 10 to 200 μm is formed on at least one surface of the polycarbonate resin sheet.

Unit (A) represented by the following formula

[In the formula (B), W is a single bond, or the following formula (W)

R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon atom. It represents an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. R ₁ and R ₂ may be bonded to form a carbocyclic or heterocyclic ring. R ₃ and R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 6 carbon atoms. Represents an aryl group of ˜12. R ₅ is an alkylene group of 1 to 9. a represents an integer of 0 to 20, and b represents an integer of 1 to 500. ]
In comprises a unit (B) represented by the unit (A) and the molar ratio of the unit (B) (A / B) is laminated body obtained by laminating a layer made of copolycarbonates 30/70 90/10. The main unit (A) is the following formula

The laminate according to claim 1, which is a unit (A1) represented by:   The laminate according to claim 1, wherein the total thickness of the laminate is 0.1 to 2.0 mm.   The laminate according to claim 1, wherein the glass transition temperature Tg of the copolymer polycarbonate is 115 ° C to 160 ° C.   The laminate according to claim 1, wherein the water absorption of the copolymer polycarbonate is 0.5% to 1.5%.   The laminate according to claim 1, wherein a hard coat layer is laminated on a layer made of a copolymerized polycarbonate.   The laminate according to claim 6, wherein the hard coat layer is formed from an ultraviolet curable coating.   The laminate according to claim 6, wherein the hard coat layer has a thickness of 1 to 20 μm.   The laminate according to claim 1, comprising 0.5 to 5.0 parts by weight of an ultraviolet absorber having a molecular weight of 350 or more with respect to 100 parts by weight of the copolymer polycarbonate.   The laminate according to claim 1, comprising 0.001 to 0.2 parts by weight of a phosphorus-based heat stabilizer with respect to 100 parts by weight of the copolymer polycarbonate.   The laminate according to claim 1, comprising 0.005 to 2.0 parts by weight of a release agent with respect to 100 parts by weight of the copolymer polycarbonate.   The laminate according to any one of claims 1 to 11, which is used as a display cover panel or a touch panel.